• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a manufacturing method of diffuse reflection film used in displays such as liquid crystal display devices, CRTs, plasma displays, and UV curable resin compositions used therein. The purpose is to provide a diffuse reflection film having a. The present invention specifically reacts a fluorine-based UV curable composition composed of a fluorine acrylate monomer, a polyfunctional thiol compound, a photopolymerization initiator and a sensitizer, a thermal polymerization inhibitor, and an organic solvent with hydrophilic silica particles, pure water, and a fluorine-based silane coupling agent under an acid catalyst. The present invention relates to an ultraviolet curable resin composition comprising a fluorine-based silica dispersion composition containing a dispersant and a solvent in a compound and a method of manufacturing a diffused reflection film using the same, wherein the diffused reflection film has excellent physical properties such as water repellency, such as a liquid crystal display device. It can be used for various applications where low reflection effect and high hardness are required.
    公开号:KR20000051532A
    申请号:KR1019990002030
    申请日:1999-01-22
    公开日:2000-08-16
    发明作者:임대우；김순식；노태환
    申请人:한형수；주식회사 새 한；
    IPC主号:
    专利说明:

    UV curable resin composition and method for producing diffuse reflection film using same {ULTRA-VIOLET HARDENING RESIN COMPOSITION AND THE PRODUCING METHOD OF THE DIFFUSELY REFLEXIVE FILM BY USING THIS ONE}
    The present invention relates to an ultraviolet curable resin composition used for a diffuse reflection film and a method for producing a film using the same, and particularly in a display device such as a liquid crystal, a cathode ray tube, a plasma display, and the like to prevent glare and scratches caused by reflection of external light. It is excellent in antifouling property, and relates to the production of an ultraviolet curable resin composition having high hardness characteristics and a diffuse reflection film using the same.
    In general, the diffuse reflection film has a function of preventing glare due to reflected light by scattering light incident from the outside. In particular, in the case of the diffuse reflection film used in the liquid crystal display device, since it is placed on the front of the liquid crystal display device, it is necessary to have a protective property against external stimulus and environmental changes, and therefore, it is important to have a scratch resistance property together with the diffuse reflection property. .
    Conventional diffuse reflection workpieces include (1) mat-shaped workpieces having irregular reflection on the surface of the substrate with uneven rollers to give diffuse reflection effect, (2) diffusion-type workpieces using a difference in compatibility or crystallinity of the resin, and (3) ) Workpieces made of thin coatings of inorganic compounds are known. However, in order to manufacture (1) of the above workpieces, the surface of the substrate must be flexible, so that scratch resistance of the surface of the substrate is inferior, and (2) changes in compatibility and crystallization characteristics of the resin according to temperature changes and solvents. There are disadvantages that can occur. In addition, the workpiece of (3) is formed by forming a thin monolayer or a multilayer inorganic thin layer on the surface of the substrate in accordance with the wavelength of the light beam, and the substrate that can be used is limited, and the process of thinning the inorganic substance requires additional apparatus and complexity. There is a disadvantage of losing.
    The present invention uses a resin system having a low refractive index in the production of a diffuse reflection film that can be mass-produced and excellent in a simple method, and particularly characterized by water repellency, oil repellency, antifouling properties with a low reflection effect that can not be exhibited in the diffuse reflection film It is for that purpose.
    The present invention is a compound in which a fluorine-based UV curable composition composed of a fluorine acrylate monomer, a polyfunctional thiol compound, a photopolymerization initiator and a sensitizer, a thermal polymerization inhibitor and an organic solvent, hydrophilic silica particles, pure water and a fluorine silane coupling agent are reacted under an acid catalyst. The present invention relates to an ultraviolet curable resin composition and a method for producing a diffuse reflection film using the same, wherein a fluorine-based silica dispersion composition containing a dispersant and a solvent is mixed.
    Hereinafter, the present invention will be described in detail.
    In the present invention, the fluorine-based UV-curable composition is prepared by containing a fluorine acrylate monomer, a polyfunctional thiol compound, a photopolymerization initiator and a sensitizer, a thermal polymerization inhibitor, an organic solvent, and the like. Examples of the fluorine acrylate monomers include trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl acrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate and hexafluoro Propyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, octylfluoropentyl acrylate, octyl fluoropentyl methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate And the like, and a refractive index usually has a range of 1.3 to 1.4.
    In the present invention, by using a multifunctional thiol-based compound to increase the UV curing sensitivity and decrease the curing shrinkage rate, the photo-curing resin composition using a thiol-based compound is oxygen at the time of curing even using a common aromatic ketone or other radical radical photoinitiator It is possible to produce a UV curable resin composition of very excellent physical properties not affected by. As such a polyfunctional thiol-based compound, those containing at least one thiol group (SH group) are typically, for example, glycol dimercaptoacetate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris ( 2-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (2-mercaptoacetate), allyl mercaptan, ethylene Glycol dimercaptopropionate, trithiocyanuric acid (1,3,5-triazine-2,4,6-tritriol), 3-dithiophenyl ether, 1,3-dimethiomethylbenzene, penta Erythritol tetrakis mercapto propionate, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-pentanedithiol, tetra methylene glycol-bis-mercapto propionate, 1,6- Bis-mercapto propionate, pentaerythritol bis mercap Topropionate, pentaerythritol tris mercapto propionate, trimethylolpropane bismercapto propionate, trimethylolpropane propionate, dipentaerythritol trimercapto propionate, sorbitol trismercapto propionate, Sorbito tetrakis mercapto propionate, sorbitol hexakis mercapto propionate, dithioethyl terephthalate, 1,6-hexanediol dithioethyl ether, 1,5-pentanediol dithioethyl ether, pentaerythritol Tetra- (beta-thioethyl ether) and the like. As the crosslinking mechanism of the thiol-based compound, the polyfunctional polythiol and the polyene compound in the photosensitive portion react to form a linear and three-dimensional network structure. In particular, the crosslinking mechanism has no decrease in the release time due to oxygen, and thus, in the air. There is a big advantage to realize high sensitivity photocurability.
    As a photoinitiator and a sensitizer, one or more compounds, such as a benzophenone, an acetophenone series, and a thioxanthone type, can be mixed and used, As a specific example, benzyl, benzoin, benzoyl methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, benzoin isobutyl ether, 4,4-dimethoxybenzyl (p-anisyl), 1,4-dibenzoylbenzene, 4-benzoylbiphenyl, 2-benzoylnaphthalene, 1-hydroxycyclohexylphenyl Ketone, benzyldimethyl ketal, benzyldiethyl ketal, benzyldimethoxyethyl ketal, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt -Butyltrichloroacetophenone, pt-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, α, α-dimethoxy-α-hydroxy acetophenone, 1- (4-isopropylphenyl) -2-hydro Hydroxy-2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -propanone, methyldiethane Amine, triethanolamine, 4,4'-dichlorobenzophenone, methyl o-benzoylbenzoate, 3,3'-dimethyl-2-methoxybenzophenone, 4-benzoyl-4 'methylphenyl, thioxanthone, 2-chlorothione Orcanthone, 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-ethyl anthraquinone, 2-propylanthraquinone, 2,2-dichloro-4-phenoxyacetophenone, 2-methyl-1- [4- (ethylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid methyl ester, p-dimethylaminobenzoic acid Ethyl ester, p-dimethylamino benzoic acid butyl ester, p-dimethylamino benzoic acid isopentyl ester, o-dimethylamino benzoic acid ethyl ester, p-dimethylaminoacetophenone, 4,4-dimethylami Nobenzophenone, 4,4'-diethylaminobenzophenone, 9-fluoroenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9 -Antron, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro- 9,10-anthraquinone, xanthone, 2-methyl-xanthone, 2-methoxy xanthone, dibenzalactone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p- Methylstyrylketone, p- (dimethylamino) benzophenone (or micelle ketone), p- (diethylamino) benzophenone, benzanthrone, benzothiazole compound, 10-butyl-2-chloroacridone, 2 , 2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-chlorophenyl) -4,5 , 4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole. In addition, by adding small amounts of phosphine and phosphate compounds as sensitizers, the photopolymerization rate can be effectively increased. Specific examples thereof include tri-o-tolylphosphine, tri-m-tolylphosphine, and tri-p-tolylphosphine. Pin, tritolyl phosphate and the like. The compounds in particular have a great influence on the improvement of the mechanical properties of the cured resin, that is, they can significantly increase the glass transition temperature of the cured resin and can almost completely eliminate the photopolymerization inhibitory effect of oxygen. On the other hand, in the present invention, a small amount of hydroquinone, hydroquinone monomethyl ether, or the like is added as a polymerization inhibitor for acid generation photoinitiators such as onium salts and triazine derivatives or storage stability, or benzimidazole and 2-mercapto as adhesion promoters. Benzimidazole, benzthiazole, 2-mercapto benzthiazole, benzoxazole, 2-mercapto benzoxazole, benztriazole and the like can be added in small amounts. The use of the adhesive enhancer as described above can be obtained an effect of improving the adhesion to the substrate after the coating, drying, exposure process.
    As the low refractive index fluorine silane coupling agent, trifluoropropyltrimethoxysilane, trifluoropropyltrichlorosilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecylmethyldichlorosilane, heptadecafluorodecyl Trimethoxysilane, heptadecafluorodecyltrichlorosilane, tridecafluorohexylethyltrimethoxysilane, tridecafluorohexylethyltrichlorosilane and the like are used, and the refractive index is usually in the range of 1.3 to 1.4. In the present invention, hydrophilic silica and a small amount of water are added to the compound under acidic catalysts such as hydrochloric acid and nitric acid at an equivalent ratio, and reacted for several hours in a few minutes in a range of 100 ° C. at room temperature, to prevent gelation of the compound resulting from the reaction. In order to secure storage stability by adding an appropriate amount of ion exchange resin to remove residual acid, a polyacrylic or polyurethane dispersant having an amine value of 10 to 60 mgKOH / g and an acid value of 8 to 80 (mgKOH / g) is used. To 1 part by weight to 20 parts by weight relative to the silica and dispersed in a bead mill disperser to obtain a fluorine-based silica dispersion composition.
    Thus, in the present invention, the silica particles are used to improve the hardness of the cured film and to give a diffuse reflection effect by the fine roughness on the surface, wherein the silica particles used in the silica dispersion composition are made of silicon dioxide, It is appropriate to have an amorphous and porous property, the shape of the particles is spherical, and the size of the silica particles is preferably 5nm ~ 1㎛. When the size of the particles is larger than 1 μm, there is a problem that the surface state of the coating film becomes rough and transparency is poor. As a method used to improve the dispersibility of silica particles, there are milling methods such as a ball mill and a sand mill. In addition, since the dispersion stability should be excellent so that the dispersion state of the particles can be maintained after dispersing the silica particles, a dispersant is used. The solvent used in the silica dispersion composition is isopropyl alcohol, methyl ethyl ketone, toluene, ethyl acetate, It may be used alone or mixed with butyl acetate and the like.
    The solvent used as the diluent in the present invention is an organic solvent added to adjust the viscosity and the solid content of the coating solution, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone and the like can be used alone or in combination.
    In the present invention, a diffuse reflection film is prepared as follows using the above composition. First, the ultraviolet curable resin composition is prepared so as to have a ratio of 20 to 80 parts by weight of the ultraviolet curable fluorinated acrylic monomer, 0.1 to 10 parts by weight of the polyfunctional thiol compound, 0.1 to 10 parts by weight of the photopolymerization initiator, and 10 to 70 parts by weight of the solvent. The fluorine-based silica dispersion composition was reacted at room temperature to 100 ° C. for several hours with 0.2 to 10 parts by weight of fluorine-based silane coupling agent, 5 to 30 parts by weight of hydrophilic silica particles, and 1 to 10 parts by weight of ultrapure water adjusted to pH 4 or less. Next, if necessary, the ion exchange resin is added, stirred for several hours, filtered, and prepared in such a way that the dispersant is 0.1 to 5 parts by weight and the solvent is 10 to 75 parts by weight. At this time, the mixing ratio of the silica dispersion composition to the ultraviolet curable resin composition is determined according to the low reflection, hardness and the degree of diffuse reflection effect of the desired transparent film, and the viscosity of the composition (Brookfield viscosity at 3 to 30 cps) and the solid content The amount of the diluent added is determined to have (15 to 80 parts by weight), and it is preferable to use about 10 to 70 parts by weight of the silica dispersion composition and about 60 to 100 parts by weight of the diluent based on 100 parts by weight of the ultraviolet curable resin composition. Do. The mixed composition thus obtained is applied onto the base film, and as a coating method, a gravure coater, a reverse coater, a slot orifice coater, or the like, which is a general solution coating method, can be used, and the thickness of the film after drying is usually 10 nanometers or more. At 10 micron or less, and after heating and drying, the film is cured by irradiation with ultraviolet rays. As the base film, any film having good transparency and UV resistance, such as polyester film, polycarbonate film, polyacryl film, and polyamide film, may be used, and triacetate used as a protective film for a polarizing plate which is a component of a liquid crystal display device. Cellulose (TAC) films are also possible.
    Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, wherein the method for evaluating the physical properties of the produced film has a haze indicating the transmittance of the film and the degree of diffuse reflection effect. It was measured by the Color Industry Co., Ltd .; NDH20D model), and the film's Clarity was also measured by the same device, and the glossiness was measured at 60˚ / 60˚ angle with the glossiness meter (No. 566 manufactured by Yasuda Seiki, Japan). The surface strength of the cured film was measured by a pencil hardness tester (JIS K 5041), and the evaluation of adhesion (adhesiveness) was measured by a cellophane adhesive tape according to JIS K 5400. The refractive index of the composition was measured using an Abe refractive index. Silver was measured and evaluated with a spectrophotometer.
    <Example 1-4>
    (1) Preparation of fluorine-based ultraviolet curable resin composition: fluorine-based acrylic monomer (20 parts by weight of hexafluoropropyl methacrylate, 20 parts by weight of heptadecafluorodecyl acrylate, 8 parts by weight of trifluoroethyl acrylate), polyfunctional Thiol-based compound (5 parts by weight of pentaerythritol tetrakis (3-mercaptopionate)), 3 parts by weight of photoinitiator (1-hydroxycyclohexylphenyl ketone), 44 parts by weight of toluene as a solvent, UV curing type A resin composition was prepared.
    (2) Preparation of fluorine-based silica dispersion composition: 5 parts by weight of heptadecafluorodecyltrimethoxysilane, 20 parts by weight of silica particles (manufactured by Degussa; Aerosil 380), and a dispersant (manufactured by Efka Chemicals; 451) 4 parts by weight, 2 parts by weight of water (ultra pure water, pH 2), and 69 parts by weight of toluene were mixed uniformly and reacted at 60 ° C. for 3 hours, followed by addition of an ion exchange resin, followed by stirring for 2 hours, followed by filtering the silica dispersion composition. Prepared.
    (3) Preparation of coating liquid: Toluene was uniformly mixed in the ratio as shown in Table 1 with the fluorine-based silica dispersion composition prepared in (2) and the diluent based on 100 parts by weight of the fluorine-based ultraviolet curable resin composition prepared in (1), This was passed through a 50 μm filter to prepare a coating solution.
    The coating solution prepared in (3) above was coated on a triacetate cellulose film at a line speed of 10 to 30mpm using a gravure coater, dried at 80 to 90 ° C, and then to an ultraviolet lamp (high pressure mercury lamp; 80 to 160 W / cm). Was irradiated to prepare a transparent film with a cured coating film. The physical properties of this film were evaluated and shown in Table 1.
    <Comparative Example 1-2>
    In the above embodiment, dipentaerythritol hexaacrylate was added to the general acrylic monomer instead of the fluorine-based acrylic monomer in the preparation of the ultraviolet curable resin composition, and heptadecafluorodecyltrimethoxysilane was prepared in the preparation of the silica dispersion composition. Was added without silica and the silica was used under the same conditions, and the others were evaluated under the same conditions.
    divisionExample 1Example 2Example 3Example 4Comparative Example 1Comparative Example 2 FurtheranceUV curable resin composition100100100100100100 Silica dispersion composition103050701030 diluent657585956575 Propertiesreflectivity(%)1.11.21.31.42.22.1 Refractive index1.3371.3451.3661.4001.4641.478 Transmittance (%)939291909291 Haze (%)102737451026 Glossiness553023205530 Surface strength3H4H4H5H2H2H AdhesionGoodVery goodVery goodGoodusuallyusually Water repellencyGoodVery goodVery goodGoodnonenone Oil repellentGoodVery goodVery goodGoodnonenone AntifoulingGoodVery goodVery goodGoodnonenone
    As shown in the above examples and comparative examples, the film obtained according to the present invention has a low reflectance due to the resin of low refractive index, and at the same time has a good hardness and diffuse reflection effect due to the cured film containing silica particles, and a fluorine-based film as the cured film. As acrylic resin is used, it shows excellent water-repellency, oil-repellency, and fouling resistance as well as chemical resistance and durability, so it can be applied to various places where low reflection effect and high hardness are required such as liquid crystal display device. Characteristics.
    权利要求:
    Claims (4)
    [1" claim-type="Currently amended] Acid-catalyzed hydrophilic silica particles, pure water and fluorine silane coupling agent with respect to 100 parts by weight of a fluorine-based ultraviolet curable composition prepared by adding a fluorine acrylate monomer, a polyfunctional thiol compound, a photopolymerization initiator and a sensitizer, a thermal polymerization inhibitor and an organic solvent. An ultraviolet curable resin composition comprising 10 to 70 parts by weight of a fluorine-based silica dispersion composition and 60 to 100 parts by weight of a diluent to a compound reacted under a dispersant and a solvent.
    [2" claim-type="Currently amended] According to claim 1, wherein the ultraviolet curable composition is 20 to 80 parts by weight of the fluorine-based acrylate monomer, 0.1 to 10 parts by weight of the thiol-based compound, 0.1 to 10 parts by weight of the photopolymerization initiator, characterized in that consisting of 10 to 70 parts by weight of the solvent, characterized in that UV curable resin composition.
    [3" claim-type="Currently amended] According to claim 1, wherein the silica dispersion composition is 0.1 to 5 parts by weight of the dispersant and 10 to 10 parts by weight of pure water and 0.2 to 10 parts by weight of the fluorine-based silane coupling agent to the compound reacted under 5 to 30 parts by weight of the hydrophilic silica particles. Ultraviolet cured resin composition, characterized in that obtained by addition to ~ 75 parts by weight.
    [4" claim-type="Currently amended] A coating liquid containing 10 to 70 parts by weight of a silica dispersion composition and a diluent in a range of 60 to 100 parts by weight based on 100 parts by weight of the ultraviolet curable composition is applied onto a base film, and irradiated with ultraviolet rays after drying to cure the coating film. Method for producing a diffuse reflection film.
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    同族专利:
    公开号 | 公开日
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-01-22|Application filed by 한형수, 주식회사 새 한
    1999-01-22|Priority to KR1019990002030A
    2000-08-16|Publication of KR20000051532A
    优先权:
    申请号 | 申请日 | 专利标题
    KR1019990002030A|KR20000051532A|1999-01-22|1999-01-22|Ultra-violet hardening resin composition and the producing method of the diffusely reflexive film by using this one|
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